Related papers: An Improved Ehrenfest Approach to Model Correlated…
Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as…
We develop a density matrix formalism to describe coupled electron-nuclear dynamics. To this end we introduce an effective Hamiltonian formalism that describes electronic transitions and small (quantum) nuclear fluctuations along a…
Trajectory-based mixed quantum-classical approaches to coupled electron-nuclear dynamics suffer from well-studied problems such as the lack of (or incorrect account for) decoherence in the trajectory surface hopping method and the inability…
An accurate description of nonadiabatic dynamics of molecular species on metallic surfaces poses a serious computational challenge associated with a multitude of closely-spaced electronic states. We propose a mixed quantum-classical scheme…
The dynamics of an electronic system interacting with an electromagnetic field is investigated within mixed quantum-classical theory. Beyond the classical path approximation (where we ignore all feedback from the electronic system on the…
The exact nuclear time-dependent potential energy surface arises from the exact decomposition of electronic and nuclear motion, recently presented in [A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 (2010)]. Such…
We consider the dynamics of interacting quantum and classical systems in the Heisenberg representation. Unlike the usual construction in standard quantum mechanics, mixed quantum-classical systems involve the interplay of unitary operators…
Ehrenfest dynamics is a useful approximation for ab initio mixed quantum-classical molecular dynamics that can treat electronically nonadiabatic effects. Although a severe approximation to the exact solution of the molecular time-dependent…
Experiments indicate that collective coupling of molecular ensembles to confined optical modes can modify excited-state dynamics and photochemical reactivity. To describe such cavity-induced effects at atomic resolution, semi-classical…
One key challenge in the study of nonadiabatic dynamics in open quantum systems is to balance computational efficiency and accuracy. Although Ehrenfest dynamics (ED) is computationally efficient and well-suited for large complex systems, ED…
We present a comprehensive computational framework for simulating nonadiabatic molecular dynamics with explicit inclusion of geometric phase (GP) effects. Our approach is based on a generalized two-level Hamiltonian model that can represent…
We investigate detailed balance for a quantum system interacting with thermal radiation within mixed quantum-classical theory. For a two-level system coupled to classical radiation fields, three semiclassical methods are benchmarked: (1)…
Ehrenfest Dynamics combined with real-time time-dependent density functional theory has proven to be a reliable tool to study non-adiabatic molecular dynamics with a reasonable computational cost. Among other possibilities, it allows for…
We discuss the evolution of purity in mixed quantum/classical approaches to electronic nonadiabatic dynamics in the context of the Ehrenfest model. As it is impossible to exactly determine initial conditions for a realistic system, we…
We present a novel quantum-classical approach to non-adiabatic dynamics, deduced from the coupled electronic and nuclear equations in the framework of the exact factorization of the electron-nuclear wave function. The method is based on the…
We benchmark a set of quantum-chemistry methods, including multitrajectory Ehrenfest, fewest-switches surface-hopping, and multiconfigurational-Ehrenfest dynamics, against exact quantum-many-body techniques by studying real-time dynamics in…
We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum…
Mixed quantum-classical methods, such as surface hopping and Ehrenfest dynamics, have proven useful for describing molecular processes involving multiple electronic states. These methods require propagating many independent trajectories,…
We present in detail the recently derived ab-initio molecular dynamics (AIMD) formalism [Phys. Rev. Lett. 101 096403 (2008)], which due to its numerical properties, is ideal for simulating the dynamics of systems containing thousands of…
Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for…